CN110799604A

CN110799604A - Fluorinated ester compound additive for architectural coatings

Info

Publication number: CN110799604A
Application number: CN201880043186.5A
Authority: CN
Inventors: J.拉西奥; M.H.奥伯; F.J.维尔纳; H.任
Original assignee: Chemours Co FC LLC
Current assignee: Chemours Co FC LLC
Priority date: 2017-06-26
Filing date: 2018-06-11
Publication date: 2020-02-14
Anticipated expiration: 2038-06-11
Also published as: EP3645634B1; JP2020525576A; WO2019005460A1; JP7086115B2; US11518894B2; EP3645634A1; CN110799604B; US20210139716A1

Abstract

The present invention is a composition having (a) a coating base selected from the group consisting of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating; and (b) a fluorinated ester compound having a plurality of fluoroalkylsulfide groups, wherein the fluorinated ester compound has a number average molecular weight < 30,000 Da; and wherein the fluorinated group Rf is independently a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted with one or more CH2, CFH, etheroxy-O-, or combinations thereof. The fluorinated ester compound provides cleanability to the resulting coating prepared from the composition of the present invention.

Description

Fluorinated ester compound additive for architectural coatings

Technical Field

The present invention relates to a composition comprising a coating base and a fluorinated ester compound for use in architectural coating compositions, such as water-based latex paints, to provide durable surface effects.

Background

Coating compositions of interest in the present invention include alkyd coating compositions, polyurethane coating compositions, water-dispersible coating compositions, and unsaturated polyester coating compositions, typically paints, clear coats, or stains. All of the above listed coating compositions after drying or curing often exhibit low hexadecane contact angles, are easily wetted by oil, and are easily soiled. Coating compositions are described in Outlines of Paint Technology (Halstead Press, New York, NY, third edition, 1990) and Surface Coatings Vol.I, Raw Materials and therir Usage (Chapman and Hall, New York, NY, second edition, 1984).

Water-based latex paint binders, such as those used as paint coatings, have a tendency to have low oil repellency and poor cleanability ratings. To impart better cleanability to interior and exterior paint surfaces, small molecule additives, including fluorosurfactants, have been used. However, this additive does not provide long term performance and durability in exterior paints subjected to more extreme environmental conditions. The additive may elute from the coating surface within a few days.

Disclosure of Invention

The present invention solves the above problems by introducing a fluorinated ester compound. The compound is small enough to migrate to the surface of the coating when wet, but stable enough to fit into components that are subject to roughness. The thioether groups of the fluorinated ester compounds of the present invention provide hydrolytic stability that provides performance benefits over known fluorinated ester compounds. The compositions of the present invention provide performance and durability to water-based latex coatings. They impart unexpected desirable surface effects such as: imparting increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating film.

The present invention relates to a composition comprising (a) a coating base selected from the group consisting of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating or an unsaturated polyester coating; and (b) a fluorinated ester compound having a plurality of fluoroalkylsulfide groups, the fluorinated ester compound selected from formula (I), formula (II), formula (III), or formula (IV):

wherein the number average molecular weight of the fluorinated ester compound is less than or equal to 30,000 Da; r¹Is straight-chain or branched C₁To C₄An alkyl group; t is an integer from 2 to 4; n is an integer not less than 3; x is independently an integer from 1 to 4; y is independently an integer from 1 to 10; y is a divalent, trivalent or tetravalent linear or branched organic linking group selected from linear or branched C1 to C₂₀Alkylene groups, carbonyl groups, thioether groups, aryl groups, cycloalkyl groups, ether groups, hydroxyl groups, -NHC (O) -, uretdione, allophanate, isocyanurate, and mixtures thereof; and R is_fIndependently a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more CH₂CFH, etheroxy-O-, or combinations thereof.

The present invention also includes an article comprising a substrate and a dried coating thereon, wherein the dried coating is formed from a drying groupA composition comprising (a) a coating base selected from the group consisting of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating; and (b) a fluorinated ester compound having a plurality of fluoroalkylsulfide groups, the fluorinated ester compound selected from formula (I), formula (II), formula (III) or formula (IV), wherein the fluorinated ester compound has a number average molecular weight of 30,000Da or less; r¹Is straight-chain or branched C₁To C₄An alkyl group; t is an integer from 2 to 4; n is an integer not less than 3; x is independently an integer from 1 to 4; y is independently an integer from 1 to 10; y is a divalent, trivalent or tetravalent linear or branched organic linking group selected from linear or branched C₁To C₂₀Alkylene groups, carbonyl groups, thioether groups, aryl groups, cycloalkyl groups, ether groups, hydroxyl groups, -NHC (O) -, uretdione, allophanate, isocyanurate, and mixtures thereof; and R is_fIndependently a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more CH₂CFH, etheroxy-O-, or combinations thereof.

Detailed Description

Trade names herein are shown in upper case.

The terms "(meth) acrylic" or "(meth) acrylate" refer to methacrylic and/or acrylic and methacrylate and/or acrylate, respectively; and the term (meth) acrylamide refers to methacrylamide and/or acrylamide.

As used hereinafter, the term "alkyd coating" refers to conventional liquid coatings based on alkyd resins, typically paints, clear coats, or stains. Alkyd resins are complex branched and crosslinked polyesters containing unsaturated aliphatic acid residues.

As used hereinafter, the term "polyurethane coating" refers to conventional liquid coatings based on type I polyurethane resins, typically lacquers, clear coatings, or stains. Polyurethane coatings typically contain the reaction product of a polyisocyanate (typically toluene diisocyanate) and a polyol ester of a drying oleic acid. Polyurethane coatings are classified into five categories by ASTM D16. The polyurethane I coatings contain a minimum of 10% by weight of a pre-reacted autoxidisable binder, characterised by the absence of a significant amount of free isocyanate groups. These are also known as polyurethane alkyds (uralkyds), polyurethane modified alkyds, oil modified polyurethanes, polyurethane oils, or polyurethane alkyds (urethane alkyds). The type I polyurethane coating is the largest class of polyurethane coatings and includes lacquers, clear coatings, or stains. The cured coating of the polyurethane I coating is formed by air oxidation and polymerization of unsaturated drying oil residues in the binder.

As used hereinafter, the term "unsaturated polyester coating" refers to a conventional liquid coating based on an unsaturated polyester resin, which is dissolved in monomers and contains initiators and catalysts as needed, typically as a paint, clear coat, stain, or gel coat formulation.

As used herein, the term "water-dispersible coating" refers to a surface coating intended to decorate or protect a substrate, consisting essentially of an emulsion, latex, or suspension of film-forming material dispersed in an aqueous phase, and optionally containing surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, defoamers, pH adjusters, coalescing aids, and other ingredients. Examples of water-dispersible coatings include, but are not limited to, pigmented coatings such as latex paints, unpigmented coatings such as wood sealants, stains and finishes, coatings for masonry and cement, and water-based asphalt emulsions. For latex paints, the film-forming material is a latex polymer of an acrylate acrylic, styrene acrylic, ethylene acrylic, vinyl or mixtures thereof. Martens describes such water-dispersible coating compositions by c.r. in Emulsion and water-Soluble Paints and Coatings "(Reinhold Publishing Corporation, New York, NY, 1965).

As used herein, the term "coating binder" refers to a liquid formulation of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating, which is subsequently applied to a substrate for forming a durable film on the surface. The coating base comprises those solvents, pigments, fillers, and functional additives that are present in conventional liquid coatings. For example, the coating binder formulation may include a polymer resin and pigment dispersed in water, wherein the polymer resin is an acrylic polymer latex, an ethylene-acrylic polymer, a vinyl polymer, a polyurethane type I polymer, an alkyd polymer, an epoxy polymer, or an unsaturated polyester polymer or mixtures thereof.

wherein the number average molecular weight of the fluorinated ester compound is less than or equal to 30,000 Da; r¹Is straight-chain or branched C₁To C₄An alkyl group; t is an integer from 2 to 4; n is an integer not less than 3; x is independently an integer from 1 to 4; y is independently an integer from 1 to 10; y is a divalent, trivalent or tetravalent linear or branched organic linking group selected from linear or branched C₁To C₂₀Alkylene groups, carbonyl groups, thioether groups, aryl groups, cycloalkyl groups, ether groups, hydroxyl groups, -NHC (O) -, uretdione, allophanate, isocyanurate, and mixtures thereof; and R is_fIndependently a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more CH₂CFH, etheroxy-O-, or combinations thereof.

The term "Y" is a divalent, trivalent or tetravalent linear or branched organic linking group selected from linear or branched C₁To C₂₀Alkylene groups, carbonyl groups, thioether groups, aryl groups, cycloalkyl groups, ether groups, hydroxyl groups, -nhc (o) -, uretdione, allophanate, isocyanurate, and mixtures thereof ", which means that Y is an organic group composed of the functional groups in any order. In formulas (I) through (IV), Y is attached to a plurality of fluorinated ester substituents having a hydrolytically stable thioether group. In one aspect, the fluorinated ester compound is selected from formula (I) and t is 2 or 3. In another aspect, t is 2. In one aspect, the fluorinated ester compound is selected from formula (II), (III) or (IV), and n is 3 to 50; in another aspect, n is 3 to 30; and in a third aspect, n is 3 to 15.

As stated previously, the number average molecular weight (M) of the fluorinated ester compound_n) Less than or equal to 30,000 Da. In one aspect, M of the fluorinated ester compound_n1000Da to 20,000 Da; and in another aspect, M_nIs 1000Da to 10,000 Da. The compound of formula (I) has a single molecular weight (no molecular weight distribution), and M can be determined by identifying the chemical structure and calculating the molecular weight from the sum of the elements_n. For compounds having a molecular weight distribution, including polymer structures of formula (II), (III) or (IV), M can be measured by Size Exclusion Chromatography (SEC)_n. Can be prepared by dissolving the compound in a deuterated solvent (such as deuterated chloroform) and performing¹HNMR to confirm the chemical structure. SEC can be performed by Gel Permeation Chromatography (GPC) equipped with a differential refractive detector and using polystyrene standards.

As the number of fluorinated branches increases, the compound becomes less soluble in water. In one embodiment, the fluorinated ester compound is water insoluble. In one aspect, the composition comprises a mixture of two or more different fluorinated ester compounds represented by formula (I), (II), (III), or (IV).

In formulae (I) to (IV), Y may be a divalent, trivalent or tetravalent organic group. Each fluorinated ester compound of formula (la) is formed from a linking organic group Y, a quaternary carbon-containing group such as a trialkanol alkane, and a fluorinated thioether group. Formula (I) is a non-polymeric compound having a valence of t on the organic group Y and 2t fluorinated thioether branches. Formula (II) is a polymeric fluorinated ester wherein Y is divalent and the quaternary carbon is part of the polymer backbone wherein the repeat unit contains a pendant fluorinated thioether group. Formula (III) is a polymeric fluorinated ester wherein Y is trivalent, wherein one ether oxygen-O-at the head of the repeat unit is attached to Y at the tail of the repeat unit, and wherein the repeat unit contains two quaternary carbons and two pendant fluorinated thioether groups. Formula (IV) is a polymeric fluorinated ester wherein Y is tetravalent wherein one ether oxygen-O-at the head of a repeat unit is attached to one Y bond from the tail of another repeat unit, each repeat unit in the polymer backbone has two quaternary carbons and has two pendant fluorinated thioether groups.

In one embodiment, the fluorinated ester compound is the reaction product of a quaternary carbon-containing polyol, a fluorinated iodide, a thioalkanoic acid, and a mercapto-or hydroxyl-reactive compound. A process for forming fluorinated ester compounds includes reacting a quaternary carbon-containing polyol with a thioalkanoic acid in the presence of a solvent or other mercapto-reactive compound to form a thioacetal, followed by reaction with a fluorinated iodide to form the final product. In this case, Y is derived from a mercapto-reactive compound and a thioalkanoic acid structure. In another method, the fluorinated iodide is reacted with a thioalkanoic acid to form a fluorinated thioalkanoic acid that is reacted with a quaternary carbon containing polyol to form a hydroxyl functionalized fluorinated diester. The hydroxyl-functionalized fluorinated diester is then reacted with a compound having two hydroxyl-reactive functional groups, such as oxalyl halide, to form the final product. In this embodiment, Y is derived from a hydroxyl-reactive compound. In one embodiment, the quaternary carbon-containing polyol has at least 3 hydroxyl groups. Common quaternary carbon-containing polyols include, but are not limited to, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, glycerol, tetra-ester polyols, and mixtures thereof. Common thioalkanoic acids include, but are not limited to, 3-thiopropionic acid, 2-thioglycolic acid, and mixtures thereof. Thioacetal products such as trimethylolpropane tris (3-mercaptopropionate) are also readily available. Thiol-reactive compounds and solvents include, but are not limited to, methyl isobutyl ketone (MIBK), methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, acetone, benzophenone, acetophenone, benzyl methyl ketone, and mixtures thereof. Hydroxyl reactive compounds include, but are not limited to, oxalyl chloride, polyisocyanates (including, but not limited to, diisocyanates or triisocyanates), and mixtures thereof.

Where the hydroxyl-reactive compound is a polyisocyanate, any polyisocyanate having two or more isocyanate groups is suitable for use in the present invention. For example, hexamethylene diisocyanate and hexamethylene diisocyanate homopolymers are suitable for use herein and are commercially available. It will be appreciated that minor amounts of diisocyanate may remain in the product having multiple isocyanate groups. An example of this is a biuret containing a small amount of hexamethylene diisocyanate residue. Also suitable for use as the polyisocyanate reactant are hydrocarbon diisocyanate-derived isocyanurate trimers, including DESMODUR N-100 (hexamethylene diisocyanate available from Bayer Corporation, Pittsburgh, Pa., USA). Other triisocyanates which can be used for the purposes of the present invention are those obtained by reacting three moles of toluene diisocyanate. The isocyanurate trimer of toluene diisocyanate and the isocyanurate trimer of 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate are other examples of triisocyanates useful for the purposes of this invention, as is methane-tris- (phenyl isocyanate). DESMODUR N-3300, DESMODUR N-3600, DESMODUR Z-4470, DESMODUR H, DESMODUR N3790 and DESMODUR XP2410 and bis- (4-isocyanatocyclohexyl) methane available from Bayer Corporation, Pittsburgh, Pa. These compounds may contain a biuret structure and may contain both aliphatic and aromatic substituents. Suitable structures include hexamethylene diisocyanate homopolymers such as DESMODUR N-100, DESMODUR N-75 and DESMODUR N-3200 available from Bayer Corporation of Pittsburgh, Pa., USA; 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate available from, for example, DESMODUR I (Bayer Corporation); bis- (4-isocyanatocyclohexyl) methane, available for example as DESMODUR W (Bayer Corporation), and diisocyanate trimers of the formulae (Va), (Vb), (Vc) and (Vd):

diisocyanate trimers (Va to Vd) are available, for example, as DESMODUR Z4470, DESMODUR IL, DESMODURN-3300 and DESMODUR XP2410, respectively, from Bayer Corporation.

The term "residue from the polyisocyanate" defines the part of the polyisocyanate compound obtained when the-NCO groups are removed. For example, in the structure OCN- (CH)₂)₆in-NCO, the residue A will be- (CH)₂)₆-. Such residues are of at least divalent structure (including divalent, trivalent, or tetravalent) and may include functional groups such as straight or branched C₁To C₂₀Alkylene groups, aryl groups, cycloaliphatic groups, allophanate groups, uretdione groups, isocyanurate groups, iminooxadiazinedione groups or mixtures thereof. In this case, uretdione, allophanate, isocyanurate and iminooxadiazinedione groups result from the dimerization, trimerization or polymerization of polyisocyanates.

The fluorinated ester compound has a plurality of fluoroalkyl sulfide groups as terminal groups. These end groups are part of a non-polymeric branched structure or are pendant from polymeric repeat units. In one embodiment, R_fIs a linear or branched perfluoroalkyl radical of 4 to 12 carbon atoms, optionally interrupted by one or more-CH₂-, -CFH-, etheroxy-O-, or combinations thereof; in another embodiment, R_fIs a linear or branched perfluoroalkyl radical of 4 to 6 carbon atoms, optionally interruptedHaving one or more-CHs₂-, -CFH-, etheroxy-O-, or combinations thereof. Examples of fluorinated iodides useful in forming fluorinated ester compounds include, but are not limited to, C₄F₉(CH₂)₂OH、C₆F₁₃(CH₂)₂I、C₈F₁₇(CH₂)₂I、C₄F₉I、C₆F₁₃I、C₈F₁₇I、C₄F₉CH₂CH₂CH₂I、C₆F₁₃CH₂CH₂CH₂I、C₄F₉CH₂I、C₆F₁₃CH₂I、C₄F₉CH₂CF₂CH₂CH₂I、C₆F₁₃CH₂CF₂CH₂CH₂I、C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂I、C₆F₁₃CH₂CF₂CH₂CF₂CH₂CH₂I、C₃F₇OCF₂CF₂CH₂CH₂I、C₂F₅OCF₂CF₂CH₂CH₂I、CF₃OCF₂CF₂CH₂CH₂I、C₃F₇(OCF₂CF₂)₂CH₂CH₂I、C₂F₅(OCF₂CF₂)₂CH₂CH₂I、CF₃(OCF₂CF₂)₂CH₂CH₂I、C₃F₇OCHFCF₂OCH₂CH₂I、C₂F₅OCHFCF₂OCH₂CH₂I、CF₃OCHFCF₂OCH₂CH₂CH₂I、C₃F₇OCHFCF₂OCH₂CH₂CH₂I、C₂F₅OCHFCF₂OCH₂CH₂CH₂I、CF₃OCHFCF₂OCH₂CH₂I、C₄F₉CH₂CH₂CF₂CF₂CH₂CH₂I、HCF₂(CF₂)₄CH₂I、HCF₂(CF₂)₆CH₂I、HCF₂(CF₂)₈CH₂I and their analogous variants.

The organic group Y is a divalent, trivalent, or tetravalent structure linking the fluorinated thioether groups together. In one embodiment, Y is selected from- (CH)₂)_zC(R²)(OH)(CH₂)_z-, C1 to C not interrupted₂₀Straight-chain or branched alkylene, -C (O) -, -C (O) - (CH)₂)_z-S-(CH₂)_r-S-(CH₂)_z-C(O)-、-C(O)-(CH₂)_z-O-(CH₂)_r-O-(CH₂)_z-C(O)-、-C(O)-(CH₂)_z-S-C(R²)(R³)-S-(CH₂)_z-C(O)-、-C(O)-₂)_z-O-C(R²)(R³)-O-(CH₂)_z-C (O) -, -C (O) NH-A-NHC (O) -; wherein z is an integer from 1 to 4; r is an integer of 1 to 20, R²Is H, straight-chain or branched C₁To C₆An alkyl group, or an aryl group; r³Is H, straight-chain or branched C₁To C₆An alkyl group, or an aryl group, and a is a residue from a polyisocyanate. In one embodiment, z is 1 to 2. In one embodiment, r is 1 to 10; and in another embodiment, r is 1 to 6. In one embodiment, R²And R³Independently is a straight or branched chain C₁To C₄An alkyl group. In another embodiment, R²And R³Both are H. In one aspect, z is 1 and R2 is H. In another aspect, z is 2, R²Is CH₃And R is³Is CH₂CH(CH₃)₂。

The fluorinated ester compound can be used as a coating additive, wherein the fluorinated ester compound can be added to a coating base, which is then applied to a substrate. The fluorinated ester compound may be added directly, or may be added as an aqueous dispersion, an aqueous emulsion, or as an organic solvent solution. In one aspect, the composition comprises the coating base in an amount of about 95 to 99.98 wt% and the fluorinated ester compound in an amount of about 0.02 to 5 wt%, based on the total weight of the coating base and the fluorinated ester compound (which equals 100%).

As noted above, the coating base is a liquid formulation of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating, which is subsequently applied to a substrate for forming a durable film on the surface. In one embodiment, the coating base is a water dispersible coating in the form of an aqueous acrylic latex paint. The coating base comprises those solvents, pigments, fillers, and functional additives that are present in conventional liquid coatings. Typically, the coating base may comprise 10 to 60 wt.% of the resin compound, 0.1 to 80 wt.% of the functional additives (including pigments, fillers, and other additives), and the remainder of the coating base composition is water or solvent. For architectural coatings, the amount of resin compound is about 30 to 60 weight percent, the amount of functional additives (including pigments, extenders, fillers, and other additives) is 0.1 to 60 weight percent, and the balance is water or solvent.

The coating composition may also comprise a pigment. Such pigments may be part of the coating base formulation, or may be added subsequently. Any pigment may be used in the present invention. As used herein, the term "pigment" means both opacifying and non-opacifying ingredients that are particulate and substantially non-volatile in use. As used herein, pigments comprise ingredients labeled as pigments, but also ingredients commonly labeled as inerts, extenders, fillers, and the like in the paint trademark.

Representative pigments useful in the present invention include, but are not limited to, rutile and anatase TiO₂Clays such as kaolin, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silica, alumina, silica, alumina,Dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fiber, glass frit, glass spheres, monostar blue G (c.i. pigment blue 15), molybdenum orange (c.i. pigment red 104), toluidine red YW (c.i. pigment 3) -process aggregated crystals (process aggregated crystals), phthalocyanine blue (c.i. pigment blue 15) -cellulose acetate dispersion, toluidine red (c.i. pigment red 3), lake red BW (c.i. pigment red 48), toluidine yellow GW (c.i. pigment yellow 1), monostar blue BW (c.i. pigment blue 15), monostar green BW (c.i. pigment green 7), pigment red (c.i. pigment red 60), gold brown (c.i. pigment brown 6), monostar green G (c.i. pigment green 7), monostar red B, monostar red GW, and phthalocyanine green 951.

Titanium dioxide (TiO)₂) Are preferred pigments for use in the present invention. The titanium dioxide pigments used in the present invention may be in the rutile or anatase crystalline form. They are generally prepared by the chloride or sulfate process. In the chloride process, TiCl₄Is oxidized to TiO₂And (3) granules. In the sulfate process, sulfuric acid and titanium-containing ore are dissolved and the resulting solution is subjected to a series of steps to produce TiO₂. Both the sulfate and chloride processes are described in more detail in John Wiley&Sons, NY (1988), "The fragment Handbook", volume 2, edition, volume 1, The teachings of which are incorporated herein by reference.

The fluorinated ester compound is effectively incorporated into the coating base through sufficient contact by, for example, mixing the composite compound composition with the coating base. The contacting of the complex compound with the coating base can be carried out, for example and conveniently, at ambient temperature. More complex contacting or mixing methods may be employed, such as using mechanical shakers or heat supply. Such methods are generally unnecessary and generally do not significantly improve the final coating composition.

The composite compounds of the present invention are typically added in an amount of about 0.02% to about 5% by weight as a percentage by weight of the dry weight of the polymer compound relative to the weight of the wet paint. In one embodiment, from about 0.02% to about 0.5% by weight of the composite compound is used, and in a third embodiment, from about 0.05% to about 0.25% by weight is added to the paint.

In another embodiment, the present invention is an article comprising a substrate and a dried coating thereon, wherein the dried coating is derived from a drying composition comprising (a) a coating binder selected from the group consisting of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I urethane coating, or an unsaturated polyester coating; and (b) a fluorinated ester compound having a plurality of fluoroalkylsulfide groups, the fluorinated ester compound selected from formula (I), formula (II), formula (III) or formula (IV), wherein the fluorinated ester compound has a number average molecular weight of 30,000Da or less; r1 is straight or branched C1 to C₄An alkyl group; t is an integer from 2 to 4; n is an integer not less than 3; x is independently an integer from 1 to 4; y is independently an integer from 1 to 10; y is a divalent, trivalent or tetravalent linear or branched organic radical selected from C₁To C₂₀Alkylene groups, carbonyl groups, thioether groups, aryl groups, ether groups, hydroxyl groups, and mixtures thereof; and R is_fIndependently a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more CH₂CFH, etheroxy-O-, or combinations thereof.

The coating compositions of the present invention can be used to provide protective and/or decorative coatings to a variety of substrates. Such substrates primarily include build materials and hard surfaces. The substrate is preferably selected from wood, metal, wallboard, masonry, concrete, fiberboard and paper. Other materials may also be used as the substrate. Any method of contacting the coating composition with the substrate can be used. Such methods are well known to those skilled in the art, such as brushing, spraying, rolling, knife coating, wiping, dipping, foaming, liquid injection, immersion or casting.

The compositions of the present invention provide performance as well as durability to the coating. They impart unexpected desirable surface effects such as: imparting increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating film. For these reasons, the compositions of the present invention are particularly useful for exterior coatings and paints.

Materials and test methods

Unless otherwise indicated, all solvents and reagents were purchased from Sigma Aldrich, st.

Perfluorohexylethyl iodide and CAPSTONE FS-61 were obtained from the Cormu corporation of Wilmington, Wilmington DE, the Chemours Company. CAPSTONE FS-61 is a partially fluorinated alcohol/P₂O₅Ammonium salts of the reaction products.

Test method

Dosing of additives in paint and test panel coating

The aqueous dispersions of the fluoroacrylic copolymers of this invention are added to selected commercially available latex paints for external use at a fluorine content of 350ppm or 1000ppm, which latex paints do not contain fluorine-containing additives prior to dosing. The samples were mixed using an overhead Cowles Blade stirrer (Cowles Blade sterrer) at 600rpm for 10 minutes. The mixture was then transferred to a glass bottle, sealed and placed on a roll mill overnight to allow the fluoropolymer to mix homogeneously. The sample was then uniformly drawn down on an aluminum Q-plate (4 '. times.12') via a BYK-Gardner draw down apparatus using a 5mL bird applicator. The paint films were then dried at room temperature for 7 days.

Test method 1: evaluation of oil repellency and Water repellency via contact Angle measurement

Oil and water contact angle measurements were used to test the migration of the fluorochemical additive to the surface of the paint film. Oil and water contact angle tests were performed by goniometer on 1 inch strips of Leneta plates coated with the dry paint film. A Standard automatic goniometer model Ram é -Hart 200, using DROPimage Standard software and equipped with an automatic dispensing system of 250 μ l syringe and an illuminated specimen stage assembly, was used. The goniometer camera is connected to the computer through an interface allowing the droplets to be observed on the computer screen. Using this software, both the horizontal axis and the orthogonal line can be adjusted independently on the computer screen.

Before measuring the contact angle, the sample is placed on the sample stage and the vertical vernier is adjusted to align the horizontal line (axis) of the eyepiece, coinciding with the horizontal plane of the sample. The stage is positioned in a horizontal position relative to the eyepiece to view one side of the test fluid droplet interface region at the sample interface.

To determine the contact angle of the test fluid on the sample, approximately one drop of the test fluid was dispensed onto the sample using a 30 μ L pipette tip and automated dispensing system to transfer a calibrated amount of the test fluid. For oil contact angle measurements, hexadecane is suitable. In the case of model 200, after leveling the sample via stage adjustment, the horizontal and orthogonal lines were adjusted via software, and the computer calculated the contact angle based on the simulated drop appearance. The initial contact angle is the angle measured immediately after dispensing the test fluid onto the sample surface. An initial contact angle of greater than 30 degrees is an indication of effective oil repellency.

The test method 2: scale resistance (DPR) test for exterior paints

The DPR test is used to evaluate the ability of painted panels to prevent fouling. An artificial dry scale consisting of silica gel (38.7%), alumina powder (38.7%), black iron oxide powder (19.35%) and lamp black powder (3.22%) was used for this test. The dust components were mixed and placed on a roller for 48 hours for thorough mixing, and stored in a desiccator.

Paint samples were drawn down onto an aluminum Q-plate, the plate was cut to 1.5 "2" size, and four parallel determinations of these samples were taped to a 4 "6" metal plate. Initial whiteness (L x) of each Q-plate was measured using a Hunter laboratory colorimeter_Initial). A 4 "x 6" metal plate was then inserted into a 45 degree angled slot in the wood frame. The dust applicator comprises a metal mesh which distributes the dust on the plate until the plate is completely covered with dust. Excess dust was then removed by tapping the plate 5 times on a wooden frame mounted inside the tray. The 4 "6" board on the dust-holding board was then clamped to Vortex-Genie 2 for 60 seconds to remove any remaining dust. The plate was then removed and tapped 10 times to remove any remaining dust. The whiteness (L x) of each 1.5 "x 2" sample was again measured using the same colorimeter_{With dust}) And the difference in whiteness before and after dust treatment was recorded. Will be provided withThe values are averaged. DPR is represented by Δ L ═ where Δ L ═ L (L ═ L_Initial-L*_{With dust}). Lower Δ L^*The values indicate better fouling resistance.

Test method 3: weathering of DPR and oil contact Angle durability (WOM)

Accelerated weathering of the coated Q-plates was carried out in ATLAS Ci5000 Xenon Lamp Weather-o-Meter. The xenon lamp was equipped with an S-type Boro inner filter and an outer filter. The weathering cycle was performed according to D6695, cycle 2. During the weathering period, the panels were subjected to a repeated 2-hour procedure, which included 18 minutes of light and water spray, followed by only 102 minutes of light. During the entire procedure, the plates were kept at 63 ℃, and during the UV-only period, the relative humidity was kept at 50%.

For the 24-hour WOM procedure, the freshly coated aluminum Q-plates were allowed to air dry for 7 days. Initial whiteness (L initial) of each Q-plate was measured using a Hunter laboratory colorimeter. One set of plates was subjected to the DPR test (per test method 2) and the oil and water contact angle test (per test method 1). The same set of plates was placed in a weather-o-meter and allowed to undergo 12 consecutive 2-hour cycles as described above. After the weathering cycle was completed, the panels were dried, evaluated according to test methods 1 and 2, and again subjected to DPR.

The following measurements were recorded: after the first artificial dry scale coating (initial), after the first artificial dry scale coating 24-hour WOM (1 day first dust), the board kept clean for 24-hour WOM and then the first artificial dry scale coating was applied (1 day new dust), the board on the 1 day first dust board was subjected to the second artificial dry scale coating (1 day second dust), the board on the 1 day second dust board was subjected to 48-hour WOM (3 day second dust) and the board on the 3 day second dust board was subjected to the third artificial dry scale coating (3 day third dust).

Test method 4: size Exclusion Chromatography (SEC)

Molecular weight and polydispersity in daltons were determined at 35 ℃ using a PL220GPC system with a differential refractive detector and a vapour light scattering detector (polymer lab). The value from the refractive index detector is selected. Column setting: three PSS 5 μm SDV, 300mm × 8mm + one PSS 5 μm guard column. HPLC grade THF (unstabilized, Omnisolv) was used as eluent at a flow rate of 1 mL/min. The molecular weight and polydispersity of the samples were calculated relative to polystyrene standards (agilent easi villis: high green, medium red and green, low yellow; calibration range, 400 daltons to 1,000,000 daltons).

Examples

Preparation example 1: fluorinated 3-thiopropionic acids

A 1-liter flask was equipped with a thermocouple, mechanical stirrer, reflux condenser, nitrogen inlet, and addition funnel. A reactor flask was charged with perfluorohexylethyl iodide (173g), isopropanol (158g), and 3-mercaptopropionic acid (42.7g), and the mixture was heated to reflux at 80 ℃. Dropwise addition of K₂CO₃An aqueous solution (57g in 83.5g water) was maintained at a temperature of 80 ℃. The mixture was kept at reflux for an additional 5.5 hours until no starting iodide could be detected. The mixture was cooled to below 40 ℃ and gradually neutralized with aqueous HCl (41g in 220g of water). The mixture was stirred at 50 ℃ for a further 15 minutes. Extracting the organic material and removing the solvent by distillation to produce Compound C₆F₁₃CH₂CH₂SCH₂CH₂COOH。

Preparation example 2: hydroxy-functionalized fluorinated diesters and dihydroxy-functionalized fluorinated monoesters

To a 200mL two-necked round bottom flask equipped with a short path distillation apparatus, nitrogen inlet, thermometer, and magnetic stir bar was added 2-ethyl-2- (hydroxymethyl) propane-1, 3-diol (5g, 37.3mmol), F from preparation example 1₁₃CH₂CH₂SCH₂CH₂COOH(33.7g，74.6mmol) and p-toluenesulfonic acid (0.300g, 1.58 mmol). The mixture was heated to 160 ℃ while the by-product water was collected in the collection flask. After six hours, the reaction was allowed to cool to room temperature and then purified by column chromatography (ethyl acetate: hexane ═ 1: 10, 1: 7.5, 1: 6, 1: 5, 1: 4). The trifluoroester (12.16g, 23%), the hydroxy-functionalized fluorinated diester (15.26g, 41%) and the dihydroxy-functionalized fluorinated monoester (3.04g, 14%) were isolated as o

Comparative example A

A calculated amount of CAPSTONE FS-61(350ppm F) was used under the same conditions as the examples for testing two exterior paints according to the test method described.

Comparative example B

The exterior paints without additives were tested according to the test method described.

Example 1

A1-L jacketed baffled reactor was equipped with a thermocouple, overhead stirrer, reflux condenser and N₂A source. Perfluorohexylethyl iodide (178.0g, rinsed with 50g of methyl isobutyl ketone) and 2-ethyl-2- (((3-mercaptopropionyl) oxy) methyl) propane-1, 3-diylbis- (3-mercaptopropionate) (50.0g, rinsed with 50g of methyl isobutyl ketone) and methyl isobutyl ketone (MIBK, 400g) were added to the reactor in this order. The mixture was stirred at room temperature. After 1.5 hours, K is added₂CO₃(69.4g) and tetrabutylammonium iodide (1.8g, 5mmol) were added to the reactor. In N₂Next, the reaction mixture was heated to 100 ℃ and stirred. The reaction mixture was concentrated in vacuo and purified on a silica column (1: 10, 1: 7, 1: 5, 1: 4 ethyl acetate: hexane as eluent). In CDCl₃In (1) on¹H NMR analysis confirmed the thioacetal structure. The final product was dispersed by dissolving 1.76g of the product in 3.3g of MIBK and adding 1.75g of a 1% sodium lauryl sulfate solution and 8.8g of water. The mixture was sonicated twice, 1m each timein, and then removing MIBK by vacuum. The dispersion was dosed at 1000ppm and tested according to the test method above.

Example 2

To a 100mL round bottom flask equipped with a nitrogen inlet and a magnetic stir bar were added the hydroxy-functionalized fluorinated diester of preparation 2 (3.7g, 3.69mmol) and dichloromethane (50 mL). The solution was cooled to 0 ℃. Oxalyl chloride (156 μ L, 1.84mmol) and triethylamine (772 μ L, 5.54mmol) were added and the mixture was stirred at 0 ℃ for 1 hour, then allowed to reach room temperature. The mixture was stirred overnight. Thereafter, the reaction mixture was partitioned with 50mL of water, and the respective layers were separated. The bottom organic layer was concentrated in vacuo and the residue was purified on a silica column (1: 5, 1: 3, 1: 1 ethyl acetate: hexanes as eluent). The oxalyl diester was collected and dispersed by dissolving in MIBK (3.18g) and adding 1% sodium lauryl sulfate solution (1.12mL) and water (4 mL). In CDCl₃In (1) on¹H NMR analysis confirmed the structure. The mixture was sonicated twice for 1min each time, and then MIBK was removed by vacuum. The dispersion was dosed at 1000ppm and tested according to the test method above.

Example 3

To a two-necked 100-mL round bottom flask equipped with an internal thermometer, reflux condenser, and nitrogen inlet was added the dihydroxy-functionalized fluorinated monoester of preparation 2 (1.455g, 2.56mmol) and 1, 6-diisocyanate (0.431g, 2.56mmol) followed by 10mL of MIBK. Iron (III) chloride (0.001g) was added to the mixture, and the mixture was heated to 80 ℃ and stirred magnetically for seven hours. Thereafter, ammonium hydroxide (337 μ L) was added and the mixture was allowed to reach room temperature while stirring. 20mL of MIBK and 20mL of water were added to the mixture, and the layers were separatedAnd (5) separating. The organic layer was concentrated and the residue was dissolved in CH₂Cl₂In (1). The solution was passed through a tampon and concentrated to give 1.79g of yellow liquid. M by test method 4_nThe measurement was 2518 Da.

For dispersion, 1.74g of the product was dissolved in methyl isobutyl ketone (MIBK, 5g) and then 1% sodium lauryl sulfate solution (1.8mL) and water (4.5mL) were added. The mixture was sonicated twice for 1min and the solvent was distilled from the dispersion. The dispersion was dosed at 1000ppm and tested according to the test method above.

Example 4

To a two-necked 100mL round bottom flask equipped with a reflux condenser, nitrogen inlet, and internal thermometer was added 1, 3, 5-tris (6-isocyanatohexyl) -1, 3, 5-triazine-2, 4, 6-trione (0.415g, 0.822mmol), the hydroxy-functionalized fluorinated diester from preparation 2 (2.472g, 2.466mmol), and methyl isobutyl ketone (10 mL). To this mixture was added iron (III) chloride (0.005g, 0.031mmol) and the final mixture was heated to 80 ℃ for 66 hours. The mixture was then cooled to room temperature and 1mL of water was added to quench the reaction. The mixture was stirred for 1 hour and concentrated under vacuum. The residue was partitioned between dichloromethane (25mL) and water (25 mL). The organic layer was filtered through a cotton plug and concentrated to give 2.82g of crude product. Purification by column chromatography (5: 1, 3: 1 hexanes: ethyl acetate) gave 0.853g of product.

In CDCl₃In (1) on¹H NMR analysis confirmed the structure. For dispersion, 0.500g of the product was dissolved in methyl isobutyl ketone (MIBK, 4g) and then 1% sodium lauryl sulfate solution (0.505mL) and water (4.2mL) were added. The mixture was sonicated twice for 1 minute each time and MIBK was removed by distillation. The dispersion was dosed at 1000ppm and tested according to the test method above.

Table 1: examples 1 to 4 and comparativeExamples A to B DPR (Δ L) Properties in exterior paints

Lower values indicate better performance.

Table 2: contact angle performance of examples 1 to 4 and comparative examples a to B in exterior paints

Higher values indicate better performance.

Claims

1. A composition comprising (a) a coating base selected from a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating or an unsaturated polyester coating; and (b) a fluorinated ester compound having a plurality of fluoroalkylsulfide groups, the fluorinated ester compound selected from formula (I), formula (II), formula (III), or formula (IV):

wherein

The number average molecular weight of the fluorinated ester compound is less than or equal to 30,000 Da;

R¹is straight-chain or branched C₁To C₄An alkyl group;

t is an integer from 2 to 4;

n is an integer not less than 3;

x is independently an integer from 1 to 4;

y is independently an integer from 1 to 10;

y is a divalent, trivalent or tetravalent linear or branched organic linking group selected from linear or branched C₁To C₂₀Alkylene groups, carbonyl groups, thioether groups, aryl groups, cycloalkyl groups, ether groups, hydroxyl groups, -NHC (O) -, uretdione, allophanate, isocyanurate, and mixtures thereof; and is

R_fIndependently a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more CH₂CFH, etheroxy-O-, or combinations thereof.

2. The composition of claim 1, wherein the composition comprises (a) the coating base in an amount of about 95 to 99.98 weight percent and (b) the fluorinated ester compound in an amount of about 0.02 to 5 weight percent, based on the total weight of (a) and (b).

3. The composition of claim 1, wherein the fluorinated ester compound is selected from formula (I) and t is 2 or 3.

4. The composition of claim 1, wherein n is 3 to 15.

5. The composition of claim 1, wherein Y is selected from- (CH)₂)_zC(R²)(OH)(CH₂)_z-, C not interrupted₁To C₂₀Linear or branched alkylene, -C (O) -, C (O) and C (O) are optionally substituted,

-C(O)-(CH₂)_z-S-(CH₂)_r-S-(CH₂)_z-C(O)-、

-C(O)-(CH₂)_z-O-(CH₂)_r-O-(CH₂)_z-C(O)-、

-C(O)-(CH₂)_z-S-C(R²)(R³)-S-(CH₂)_z-C(O)-、

-C(O)-(CH₂)_z-O-C(R²)(R³)-O-(CH₂)_z-C(O)-、-C(O)NH-A-NHC(O)-；

Wherein z is an integer from 1 to 4; r is 1 to 20Integer, R²Is H, straight-chain or branched C₁To C₆An alkyl group, or an aryl group; r³Is H, straight-chain or branched C₁To C₆An alkyl group, or an aryl group, and a is a residue from a polyisocyanate.

6. The composition of claim 5, wherein z is 1, and R²Is H.

7. The composition of claim 5, wherein z is 2, R²is-CH₃And R is³is-CH₂CH(CH₃)₂。

8. The composition according to claim 1, wherein the fluorinated ester compound (b) is water-insoluble.

9. The composition of claim 1, wherein the coating base is a water dispersible coating in the form of an aqueous acrylic latex paint.

10. The composition of claim 1, wherein the coating base comprises an additive selected from the group consisting of: TiO 2₂Clay, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silica, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fiber, glass frit, glass spheres, blue pigment, red pigment, yellow pigment, orange pigment, process aggregated crystal, brown pigment, or green pigment.

11. An article comprising a substrate and a dried coating thereon, wherein the dried coating is derived from a drying composition comprising (a) a coating binder selected from the group consisting of a water-dispersible coating, an epoxy polymer coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating; and (b) a fluorinated ester compound having a plurality of fluoroalkylsulfide groups, the fluorinated ester compound selected from formula (I), formula (II), formula (III), or formula (IV):

wherein

R¹is straight-chain or branched C₁To C₄An alkyl group;

t is an integer from 2 to 4;

n is an integer not less than 3;

x is independently an integer from 1 to 4;

y is independently an integer from 1 to 10;

12. The article of claim 10, wherein Y is selected from- (CH)₂)_zC(R²)(OH)(CH₂)_z-, C not interrupted₁To C₂₀Straight-chain or branched alkylene, -C (O) -, -C (O) - (CH)₂)_z-S-(CH₂)_r-S-(CH₂)_z-C(O)-、

-C(O)-(CH₂)_z-O-(CH₂)_r-O-(CH₂)_z-C(O)-、

-C(O)-(CH₂)_z-S-C(R²)(R³)-S-(CH₂)_z-C(O)-、

-C(O)-(CH₂)_z-O-C(R²)(R³)-O-(CH₂)_z-C(O)-、-C(O)NH-A-NHC(O)-；

Wherein z is an integer from 1 to 4; r is an integer of 1 to 20, R²Is H, straight-chain or branched C₁To C₆An alkyl group, or an aryl group; r³Is H, straight-chain or branched C₁To C₆An alkyl group, or an aryl group, and a is a residue from a polyisocyanate.

13. The article of claim 11, wherein the composition comprises (a) the coating binder in an amount of about 95 to 99.98 weight percent and (b) the fluorinated ester compound in an amount of about 0.02 to 5 weight percent, based on the total weight of (a) and (b).

14. The article of claim 11 wherein the coating base is a water dispersible coating in the form of an aqueous acrylic latex paint.

15. The article of claim 11, wherein the substrate is selected from the group consisting of wood, metal, wallboard, masonry, concrete, fiberboard, and paper.